Manufacture of fibers and foils



. polyamides.

Patented Mar. 4, 1947 2,416,890 MANUFACTURE OF FIBERS AND FOILS JoachimAmende and Willibald hafen-on-the-Rhein,

Attorney General of No Drawing.

12 Claims.

This invention relates to the manufacture of fibers and foils.

It is an object of this invention to .produce fibers and foils ofspecial properties.

A further object is to produce these fibers and foils from viscosesolutions treated with superpolyamides.

A still further object is the provision of fibers and foils fromammoniacal copper oxyde solutions treated with superpolyamides.

These and other objects will appear from the detailed specificationfollowing hereinafter. It ha been found that fibers and foils ofexcellent properties are obtained, if solutions of viscose and cellulosein ammoniacal copper oxyde treated with alkali-soluble .superpolyamidescontaining sulfamide groups, are spun or worked up into foils.Alkali-soluble superpolyamides are obtained according to the Germanpatent application I. 64,124 IVd/lZo, filed March 20, 1939, bycondensing diamines containing sulfamide groups and/or dicarboxylicacids or their functional derivatives or salts of these acids with thediamines or amino carboxylic acids containing sulfamide groups or theirfunctional derivatives, especially lactams.

According to the description in said German application, the startingmaterials containing sulfamide groups can be employed inthe quantitiesnecessary for the condensation. However, a part of these startingmaterials may be substituted by corresponding starting materials free ofsulfamide groups. It is necessary, however, that the final product havea certain content of sulfamide groups, to obtain a readyalkali-solubility. The quantity of the starting material containingsulfamide groups required for this process varies depending upon thechemical property of the starting material-and can be easily determinedby test.

The 'manufacture of the condensation products is carried out in themanner conventional for uperpolyamides, especially by heating thestarting materials to, high temperatures in the presence or in theabsence of solvents or diluents.

The superpolyamides obtained are practically colorless, resin-freesubstances which can be HOOC.

Ender, Ludwigs- Germany; vested in the the United States ApplicationApril 6,1940, Serial No.

In Germany March 29, 1939 amide (related to cellulose),

spun into filaments in the molten state in a manner similar to that usedfor the known super- The superpolyamides obtained are soluble. inaqueous alkalies in contrast to the obtained are better than those offibers and known superpolyamides which do not contain their color. Thefabrics or fib 2- sulfamide groups. Due to this property they are suitedespecially for the refining of textile fibers, particularly as sizingagents. It is likewise possible to treat fibers or fabrics of textilematerials with solutions of these superpolyamides, whereby the fibers orfabric are refined with respect to ers of cellulose filaments thustreated absorb much more easily substantive dyestuffs and can be dyedeven with acid dyestuffs, for-example wool dyestuffs, and also withacetate rayon dyestuffs.

In the present invention, solutions of viscose or of cellulose inammoniacal copper oxyde are preferably mixed with alkaline solutions ofthese superpolyamides and then spun in a known man: ner or worked upinto foils. Hereby the usual coagulation agents like salt solutions oracids may be employed. The quantity of the superpolyamides, to be givento the spinning solution, may vary within wide limits. Preferably thereare added not less than 5 per cent superpolyas otherwise the admixtureof superpolyamides is of no practical value. On the other hand amultiple of superpolyamide compared with cellulose may be employed.

The fibers obtained are faster to possess a far higherBauschelastizitat" (bolsterelasticity) and a more elastic grip thanviscosefibers. The grip, moreover, on account of the goodBauschelastizitat resembles wool. Also the dyeing properties of thefibers and foils thus foils from .pure viscose or pure ammoniacal copperoxyde cellulose. They absorb dyestuffs for instance much easier and Carlbe dyed in darker shades than pure viscose or pure ammoniacal copperoxyde cellulose. Contrary to these they may be dyed with acid dyestuffs,for instance with wool dyestuffs and also with acetate silk dyestufl's.On account of the excellent dyeing properties the fibers are very muchadapted for the manufacture of mixed fabrics.

Example I parts by weight ofN.N-di-propanecarboxacid-p-sulfo-benzoic-acid-amide Wrinkling and lowishcolor and is over, possess contrary to page 131) by adding productconsisting of soluble in a concentrated aqueous alkali solution. It canbe drawn into filaments in the molten state.

A 20 per cent solution of said superpolyamide consisting of'hexamethylenediamine and N.N-dipropane-carboxylicacid-p-sulfo-benzoic-aciddiamide in a caustic sodasolution of about 8 per cent is added to a viscose solution capable ofbeing spun in such a quantity, that after spinning and coagulatingfilaments containing about: per cent superpolyamide are obtained. Theelasticity of these filaments is far greater of pure viscose filaments.The filaments, moregrip and excellent Bauschel tizitat.

The filamentsv may be dyed is boiling one hou with 2 per cent AcidAnthfacene Red 3 BL (Schultz dyestufi tables, year 1932, vol. II, page187) ratio of the weights of filaments and water 1:50, by adding 10percent Glauber salt and 4 per cent formic acid. It is then washed withlukewarm water and afterwards dried. The shades obtained are distinctlydarker thanon viscose silk without addition of the superpolyamide,whereby the degree of fastness is for both kinds at least the same. Ifthe filaments are dyed in the same way with 2 per cent Palatine FastBlue GGN (Schultz dyestufi tables, year 1932, vol. II, page 108) byadding 6 per cent formic acid or with 2 per cent Sirius Light Blue BRR.(Schultz dyestufl" tables, year 1934, Vol.1,

also distinctly darker, but more brilliant shades are obtained than oncellulose free from superpolyamides.

' Example If 50 parts by weight of N.N'-di-propanecarboxylicacid-'diphenylether-4A'-disulfonic-aciddiamide than that A the others awool-like- 20 per cent Glauber salt,.

4 Blue BF (Cellitonechtblau' BF)... concentrated powder, ratio oftheweights of filaments and water 1:50. The shades-are far darker than,

those one filaments from superpolyamide-efree- 5 viscose solution,whereby the degree vof fastness for both kinds is very much the same.

Example III .An alkaline solution of a s'uperpolyamideconsisting of 1mol N.N-dipropanecarboxylic-acidp-sulfobenzoic-acid-diamide, 1 moladipic acid and 2 mols hexamethylenediamine is added to a viscosesolution capable of being spun in such a quantity, that the finishedfilaments contain about 20 per cent superpolyamide. The filaments aredyed by boiling one hour with 2 per cent Sirius Fast Blue (Schultzdyestufi tables, year 1934, supplementary volume I, page 131) ratio ofthe weights of filaments and water Glauber salt. Far darker shades thanon filaments consisting of superpolyamide-free viscose are thusobtained.

What we claim is:

1. A process for the foils from a mixture of an superpolyamidecontaining sulfamide groups and a cellulosic solution selected from thegroup'con- 'sisting of viscose and ammoniacal copper oxide cellulose,which comprises adding to the cellulosic solution an alkaline solutionof thesuperpolyamide, the amount of superpolyamide added to thecellulosic solution being at least 5%, based onno0o.cHi.0H,.onmnsofiogsomn.among.ontooon and 6 parts by weight ofhexamethylenediamine I are condensed as described in Example I. The

superpolyamide obtained is-soluble in an aqueous alkali solution.

An alkaline solution of said condensation N.N'dipropane-carboxylic-acid-diphenylether- 4.4. di-sulfonic-acid-diamideis added to a viscose solution as described in Example I in such aquantity, that the finished filaments spun from the solution contain 15per cent of the superpolyamide'. They are spun in the way usuallyadapted for pure viscose. The filaments are very' elastic and show awool-like grip. If they are boiled one hour with 2 per centFast-Mordant- Blue E (Schultz dyestuff tables, year 1934, supplementaryvolume I, page 90) ratio of the weights of filaments and water 1:50, byadding 10 per cent Glauber salt and 4 per cent formic acid and, ifafterwards treated for minutes with 1 per cent potassium chromate,distinctly foils can be obtained and darker shades than 0115hexamethylenediamine and 5 pane carboxylicacid-p-sulfobenzoic-acid-dilulosic solution is an ammoniacal copperoxide 45 cellulose solution. a

4. A process as' in claim 1 in which the cellulosic solution is aviscose solution and the superpolyamide is the condensation productobtained from hexamethylene diamine and N.N'-diproamide.

5. A process as in claim 1 in which the cellulosic solution is a viscosesolution and the superpolyamide is the condensation product fromhexamethylene diamine and N.N dipropane-carboxylic-acid-diphenylether-4.4'-di-sulfonic-acid-diamide..

g 6. A process as in claim 1 in which the cellulosic solution is aviscose solution and the superc0 polyamide is the condensation productobtained 1 from one mol ofN.N'-dipropane-carboxylic-acidp-sulfobenzoic-acid-diamide, one mol ofadipic acid and two mols of hexamethylene diamine.

comprising as essential polyamide containing sulfamide'groups, dissolvedin a cellulosic solution selected from the'group consisting of viscoseand ammoniacal copper 76 oxide cellulose.

BRR (Siriusechtblau BRR) 1:50, by adding 20 per cent manufacture offibers and alkali-soluble linear obtained '7. A new filament as in claim11 in which the based on the weight, of the cellulose, of analkali-soluble linear superviscose solution.

10. A spinning solution as in claim 8 in which the cellulosic solutionis viscose and the superpolyamide is the condensation product obtainedfrom hexamethylene diamine and N.N'-dipropane carboxylicacid-p-sulfobenzoic-aciddlamide.

11. A new filament comprising regenerated viscose cellulose containingat least five percent, based on the cellulose, and dissolved in theviscose solution from which the filament is formed, of an alkali-solublelinear superpolyamide containing sulfamide groups, said filament beingresistan't to wrinkling, wool-like in character and readily dyed by acidand acetate silk dyes.

12. Filaments and foils comprising essentially a mixture of regeneratedcellulose derived from a cellulosic solution selected from the groupconsisting of viscose and ammoniacal copper oxide cellulose. and atleast five percent, based on the weight of the cellulose, of analkali-soluble linear superpolyamide containing sulfamide groups. thesuperpolyamide being dissolved in the cellulosic solution, saidfilaments and foils being resistant to wrinkling, readily dyed by acidand acetate silk dyes and having been obtained by the process ofclaim 1. I

' JOACHIM AMENDE. WILIBALD ENDER.

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Martin Dec. 3, 1940

